Through a self-sacrificing template method, highly uniform hollow-spheres of TiO2 anatase are synthesized with controllable diameter from 365 nm to 930 nm. Compared to large hollow spheres, a large enhancement in the photocatalytic activity is reported for the small hollow spheres (with a thickness of 50 nm). By extending Mie's scattering theory from solid- to hollow-spheres, for a spherical scatter with a diameter of 300-900 nm, theoretical calculation reveal that each singular hollow sphere has absorption power equivalent to a solid sphere as the shell thickness parameter reaches a critical value of 0.3-0.6. This critical thickness parameter is independent to the size of a single hollow sphere, demonstrating that hollow spheres have quantitative advantages over solid spheres of the same weight. Moreover, calculation supported that small hollow spheres have stronger absorption power than large hollow spheres due to higher thickness. This greatly enhance the performance of small hollow spheres under a photocatalytic test. Our theoretical results showed good agreement to the experimental measurements, and provided a framework for the design of hollow-sphere nano-particles for optimized absorption power. (C) 2013 Elsevier B.V. All rights reserved.